CN105854745B - A method of microcapsules are prepared by polymer pre-coated - Google Patents
A method of microcapsules are prepared by polymer pre-coated Download PDFInfo
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- CN105854745B CN105854745B CN201610238903.2A CN201610238903A CN105854745B CN 105854745 B CN105854745 B CN 105854745B CN 201610238903 A CN201610238903 A CN 201610238903A CN 105854745 B CN105854745 B CN 105854745B
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- polymer
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/02—Making microcapsules or microballoons
Abstract
The invention discloses a kind of methods preparing microcapsules by polymer pre-coated comprising following steps：1）It adds a polymer in organic solvent, is uniformly mixed, obtain polymer solution, add core material, be uniformly mixed, obtain mixed solution；2）Colloid protective agent will be helped to be added to the water, be uniformly mixed, step 1 is added while stirring）Mixed solution, heating so that organic solvent is volatilized completely, obtain the microcapsules of polymer pre-coated core material；3）Wall material is added, stirring fully cures, obtains microcapsules.The method versatility of the present invention is good, easy, quick, economical, can be widely used in the preparation field of novel microcapsules；The capsule size and structure of the present invention is adjustable, moreover it is possible to and surface-functionalized modification and modification are carried out, is had excellent performance, it is economical and practical.
Description
Technical field
The present invention relates to a kind of methods preparing microcapsules by polymer pre-coated.
Background technology
Microcapsules technology has been widely used in household chemicals, food industry, biomedicine, high molecular material auxiliary agent etc.
Field.According to different needs, people can be protected using the technology and be wrapped by substance and not be affected by the external environment, improve substance
The advantages that stability, odor barrier, controlled release, is carried out target substance by natural, synthesis or semi-synthetic high molecular material
Effectively cladding.Therefore, microcapsules technology is grown rapidly in recent years, becomes a kind of effective quotient in many industry fields
Product method.
The preparation method of microcapsule product includes chemical method, physical-chemical process and Physical.During preparation, how
Make wall material effectively react to form capsule being wrapped by material surface, improves the encapsulating effect of target substance, this is to prepare
Microcapsules need the critical issue solved.In addition, major part microcapsules exist in the form of suspension when preparing microcapsules,
Particle size range is concentrated mainly between 1~500 micron, it is easy to coalescence occur, lump so as to cause microcapsules, to later product
With having an impact.Therefore, must assure that in preparation process between microcapsule granule has good dispersibility and to microcapsules
Core material is effectively coated.Coalescence occurs in microencapsulation processes between capsule particle in order to prevent, while improving encapsulating effect
Fruit is frequently added dispersant or stabilizer as microcapsules protecting colloid in reaction system.To ensure the encapsulating effect of microcapsules
And stability, generally use inorganic dispersant, natural polymer, modified natural polymer or synthesis macromolecule are as micro- glue
Capsule protecting colloid.
Great modification is made to preparing urea-formaldehyde resin microcapsule as protecting colloid using carboxylic acid family macromolecule from U.S. NCR
Afterwards, many researchers and enterprise select the high-molecular copolymers such as vinyl, maleic anhydride or compounding dispersant as microcapsules
Protecting colloid.The Chinese patent of Publication No. CN103741496A discloses a kind of using nonionic surfactant and amphiphilic
Macromolecule is prepared into composite dispersing agent, and using essential oil as core material, melamine resin is wall material, and it is micro- to prepare essence by interfacial polymerization
The method of capsule.Melamine resin is effectively moved to core surfaces and carries out polymerisation by this method, improves the packet of microcapsules
Seal effect.The Chinese patent of Publication No. CN104624127A is then using the polyvinyl alcohol and gelatin conduct for preparing proper ratio
Complex protection colloid prepares microcapsules.
The work that although method can play fine dispersion microcapsule granule, prevent particle coalescence used by above-mentioned patent
With, but they can only be directed to a certain or certain a kind of core material and be effectively disperseed, and coating other cores of different nature
When material substance, core material and wall material can not be rationally connected, is unable to reach the purpose of effectively encapsulating and storage-stable, use scope is very
It is limited.In addition, general protecting colloid can not adjust the cyst wall intensity of microcapsules according to demand.Up to the present, there are no reports
Road one kind excessively can either effectively disperse microcapsule granule, rationally bridge various microcapsules core materials to be covered of different nature and wall
Material can also control polymeric precoat layer thickness, realize the adjustable universal method of microcapsule wall material mechanical property.
Invention content
The purpose of the present invention is to provide a kind of methods preparing microcapsules by polymer pre-coated.
Another object of the present invention is to provide a kind of microcapsules.
The technical solution used in the present invention is：
A method of microcapsules are prepared by polymer pre-coated, are included the following steps：
1) it adds a polymer in organic solvent, is uniformly mixed, obtain polymer solution, add core material, stir
It mixes uniformly mixed, obtains mixed solution；
2) colloid protective agent will be helped to be added to the water, be uniformly mixed, step 1 is added while stirring）Mixed solution, rise
Temperature makes organic solvent volatilize completely, obtains the microcapsules of polymer pre-coated core material；
3) wall material is added, stirring fully cures, obtains microcapsules.
The core material, polymer, wall material mass ratio be 1：（0.2~1）：（0.5~3）.
Step 1）The mass fraction of polymer is 5~20% in the polymer solution.
Step 2）The quality for helping colloid protective agent is the 0.5~3.0% of the quality of water.
The polymer is by methyl methacrylate, ethyl acrylate, butyl acrylate, hydroxy-ethyl acrylate, acryloyl
Amine, maleic anhydride polymerize at least one of vinyl benzenesulfonic acid sodium, Sodium Allyl Sulfonate, vinyl acetate, Isooctyl acrylate monomer
It obtains.
The core material is at least one of Rosa Damascana, caryophyllus oil, wide leaves of pulse plants oil, dicyclopentadiene, paraffin.
The organic solvent is at least one of dichloromethane, chloroform, petroleum ether, tetrahydrofuran.
It is described to help colloid protective agent for dodecyl sodium sulfate, polyvinyl alcohol, polyvinyl pyrrolidone, Arabic gum, methyl
At least one of cellulose.
The wall material is at least one of sodium alginate, polystyrene, Lauxite, phenolic resin, melamine resin.
The beneficial effects of the invention are as follows：
1）The method versatility of the present invention is good, easy, quick, economical, can be used for coating the core material of various properties, according to not
The demand in field of the same trade can select the polymer formed with different structure, effectively bridge microcapsules core material to be covered and
Wall material, and effectively disperse microcapsule granule using the polymer as protecting colloid, it overcomes in current microcapsules preparation process often
The shortcomings that a certain core material or certain a kind of core material being only applicable to protecting colloid；
2）The method of the present invention polymer molecular weight can be carried out according to actual demand and dosage is adjusted, and it is pre- to prepare polymer
Coating layer thickness and the adjustable microcapsules of cyst wall mechanical property；
3）The method of the present invention can add functional functional group, therefore may be implemented by being modified to polymer
Functional modification to surface of microcapsule and modification can be widely used in the preparation field of novel microcapsules；
4）The capsule size and structure of the present invention is adjustable, moreover it is possible to and surface-functionalized modification and modification are carried out, is had excellent performance,
It is economical and practical.
Description of the drawings
Fig. 1 is the SEM image of the microcapsules of embodiment 3.
Specific implementation mode
A method of microcapsules are prepared by polymer pre-coated, are included the following steps：
1) it adds a polymer in organic solvent, is uniformly mixed, obtain polymer solution, add core material, stir
It mixes uniformly mixed, obtains mixed solution；
2) colloid protective agent will be helped to be added to the water, be uniformly mixed, step 1 is added while stirring）Mixed solution, rise
Temperature makes organic solvent volatilize completely, obtains the microcapsules of polymer pre-coated core material；
3) wall material is added, stirring fully cures, obtains microcapsules.
Preferably, a method of microcapsules are prepared by polymer pre-coated, are included the following steps：
1) it adds a polymer in organic solvent, is uniformly mixed, obtain polymer solution, add core material, stir
It mixes uniformly mixed, obtains mixed solution；
2) colloid protective agent will be helped to be added to the water, be uniformly mixed, step 1 is added while stirring）Mixed solution, then
It is heated up with the rate of 0.5~5 DEG C/min, stops heating when temperature is higher than 10~15 DEG C of solvent boiling point, keep the temperature 20~40min, obtain
To the microcapsules of polymer pre-coated core material；
3) wall material, stirring is added, 60~70 DEG C of 3~5h of curing obtain microcapsules.
Preferably, the core material, polymer, wall material mass ratio be 1：（0.2~1）：（0.5~3）.
Preferably, step 1）The mass fraction of polymer is 5~20% in the polymer solution.
Preferably, step 2）The quality for helping colloid protective agent is the 0.5~3.0% of the quality of water.
Preferably, step 1）With 2）In when being stirred the rotating speed of blender be 500~3000rpm.
Preferably, step 3）In when being stirred the rotating speed of blender be 300~1500rpm.
Preferably, the polymer by methyl methacrylate, ethyl acrylate, butyl acrylate, hydroxy-ethyl acrylate,
Acrylamide, maleic anhydride, at least one in vinyl benzenesulfonic acid sodium, Sodium Allyl Sulfonate, vinyl acetate, Isooctyl acrylate monomer
Kind is obtained by homopolymerization or copolymerization.
Preferably, the core material is at least one of Rosa Damascana, caryophyllus oil, wide leaves of pulse plants oil, dicyclopentadiene, paraffin.
Preferably, the organic solvent is at least one of dichloromethane, chloroform, petroleum ether, tetrahydrofuran.
Preferably, described to help colloid protective agent for dodecyl sodium sulfate, polyvinyl alcohol, polyvinyl pyrrolidone, Arab
At least one of glue, methylcellulose.
Preferably, the wall material be sodium alginate, polystyrene, Lauxite, phenolic resin, in melamine resin at least
It is a kind of.
The present invention is made further explanation and description with reference to specific embodiment.
Embodiment 1：
1）Beaker is added in 1.0g polymethyl methacrylates and 20.0g dichloromethane, is uniformly mixed, obtains quality
The polymethyl methacrylate dichloromethane solution that percentage is 5% is added 1.0g Rosa Damascanas, is uniformly mixed, is mixed
Close solution；
2）Into the reactor with heating device and blender, 100.0g distilled water and 0.5g polyvinyl alcohol is added
（1788）, after heating stirring is completely dissolved to polyvinyl alcohol, system temperature is down to room temperature.Then step 1 is added）Mixing it is molten
Liquid maintains speed of agitator 500rpm, so that dichloromethane is slowly volatilized with the rate heating of 5.0 DEG C/min, when temperature reaches 50.0
DEG C when, stop heat up simultaneously keep the temperature 30min, obtain the microcapsules of polymethyl methacrylate pre-coated Rosa Damascana；
3）Temperature of reaction system is down to room temperature, 0.5g gelatin is added, is stirred under the rotating speed of 300rpm, in 65 DEG C
Water-bath cures 4h, obtains the microcapsules of polymethyl methacrylate macromolecule layer bridge joint Rosa Damascana and gelatin.The microcapsules point
It is good to dissipate property, mechanical performance is high.
Embodiment 2：
1）Beaker is added in 5.0g polyacrylamides and 50.0g dichloromethane, is uniformly mixed, obtains mass percent
For 10% polyacrylamide dichloromethane solution, 10.0g caryophyllus oils are added, is uniformly mixed, obtains mixed solution；
2）Into the reactor with heating device and blender, 300.0g distilled water and 4.5g dodecyl sodium sulfonates is added
System temperature after heating stirring is completely dissolved to dodecyl sodium sulfate, is down to room temperature by sodium, and step 1 is then added）Mixing
Solution maintains blender rotating speed 1000rpm, so that dichloromethane is slowly volatilized with the rate heating of 3.0 DEG C/min, when temperature reaches
At 50.0 DEG C, stops heating up and keep the temperature 20min, obtain the microcapsules of polyacrylamide pre-coated caryophyllus oil；
3）Temperature of reaction system is down to room temperature, 10g polystyrene is added, is stirred under the rotating speed of 800rpm, in
60 DEG C of water-baths cure 5h, obtain the microcapsules of polyacrylamide macromolecule layer bridge joint caryophyllus oil and polystyrene.The microcapsules point
It is good to dissipate property, mechanical performance is high.
Embodiment 3：
1）Beaker is added in 8.0g butyl polyacrylates-acrylic acid and 40.0g chloroforms, is uniformly mixed, obtains
Butyl polyacrylate-acrylic acid chloroform soln that mass percent is 20% is added the wide leaves of pulse plants oil of 24.0g, is stirred
It is even, obtain mixed solution；
2）Into the reactor with heating device and blender, 500.0g distilled water and 15.0g polyvinyl pyrroles is added
System temperature after heating stirring is completely dissolved to polyvinyl pyrrolidone, is down to room temperature by ketone, and step 1 is then added）Mixing it is molten
Liquid maintains blender rotating speed 3000rpm, so that chloroform is slowly volatilized with the rate heating of 2.0 DEG C/min, when temperature reaches
At 72.0 DEG C, stops heating up and keep the temperature 40min, obtain the microcapsules of the wide leaves of pulse plants oil of butyl polyacrylate-acrylic acid pre-coated；
3）Temperature of reaction system is down to room temperature, 30g Lauxites are added, are stirred under the rotating speed of 1000rpm, in
70 DEG C of water-baths cure 3h, obtain that surface is smooth, spherical full butyl polyacrylate-acroleic acid macromolecular layer bridge wide leaves of pulse plants oil and
The microcapsules of Lauxite, SEM figures are as shown in Figure 1.
Embodiment 4：
1）Beaker is added in 10.0g butyl polyacrylates and 100.0g tetrahydrofurans, is uniformly mixed, obtains quality hundred
Divide than the butyl polyacrylate tetrahydrofuran solution for 10%, 40.0g dicyclopentadienes are added, is uniformly mixed, is mixed
Solution；
2）Into the reactor with heating device and blender, 700.0g distilled water and 14.0g Arabic gums is added, adds
After thermal agitation is completely dissolved to Arabic gum, system temperature is down to room temperature, step 1 is then added）Mixed solution, maintain to stir
Machine rotating speed 1500rpm is mixed, so that tetrahydrofuran is slowly volatilized with the rate heating of 0.5 DEG C/min, when temperature reaches 76.0 DEG C, stops
It only heats up and keeps the temperature 30min, obtain the microcapsules of butyl polyacrylate pre-coated dicyclopentadiene；
3）Temperature of reaction system is down to room temperature, 120g phenolic resin is added, is stirred under the rotating speed of 800rpm, in
65 DEG C of water-baths cure 4h, obtain the microcapsules of butyl polyacrylate macromolecule layer bridged bicyclic pentadiene and phenolic resin.
Embodiment 5：
1）Beaker is added in 12.0g hydroxyethyl acrylate and 120.0g petroleum ethers, is uniformly mixed, obtains quality hundred
Divide than the hydroxyethyl acrylate petroleum ether solution for 10%, 60.0g paraffin is added, is uniformly mixed, obtains mixed solution；
2）Into the reactor with heating device and blender, 700.0g distilled water and 7.0g methylcellulose is added,
After heating stirring is completely dissolved to methylcellulose, system temperature is down to room temperature, step 1 is then added）Mixed solution, dimension
Blender rotating speed 2000rpm is held, so that petroleum ether is slowly volatilized with the rate heating of 1 DEG C/min, when temperature reaches 86.0 DEG C, stops
It only heats up and keeps the temperature 30min, obtain the microcapsules of hydroxyethyl acrylate pre-coated paraffin；
3）Temperature of reaction system is down to room temperature, 180g melamine resins are added, are stirred under the rotating speed of 600rpm, in
65 DEG C of water-baths cure 4h, obtain the microcapsules of hydroxyethyl acrylate macromolecule layer bridge joint paraffin and melamine resin.The microcapsules
Surface is smooth, good dispersion and cyst wall have certain elasticity.
The above embodiment is a preferred embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment
Limitation, it is other it is any without departing from the spirit and principles of the present invention made by changes, modifications, substitutions, combinations, simplifications,
Equivalent substitute mode is should be, is included within the scope of the present invention.
Claims (10)
1. a kind of method preparing microcapsules by polymer pre-coated, it is characterised in that：Include the following steps：
1) it adds a polymer in organic solvent, is uniformly mixed, obtain polymer solution, add core material, stirring is mixed
It closes uniformly, obtains mixed solution；
2) colloid protective agent will be helped to be added to the water, be uniformly mixed, step 1 is added while stirring）Mixed solution, heating makes
Organic solvent volatilizees completely, obtains the microcapsules of polymer pre-coated core material；
3) wall material is added, stirring fully cures, obtains microcapsules.
2. a kind of method preparing microcapsules by polymer pre-coated according to claim 1, it is characterised in that：It is described
Core material, polymer, wall material mass ratio be 1：（0.2~1）：（0.5~3）.
3. a kind of method preparing microcapsules by polymer pre-coated according to claim 1 or 2, it is characterised in that：
Step 1）The mass fraction of polymer is 5~20% in the polymer solution.
4. a kind of method preparing microcapsules by polymer pre-coated according to claim 3, it is characterised in that：Step
2）The quality for helping colloid protective agent is the 0.5~3.0% of the quality of water.
5. a kind of method preparing microcapsules by polymer pre-coated according to claim 4, it is characterised in that：It is described
Polymer by methyl methacrylate, ethyl acrylate, butyl acrylate, hydroxy-ethyl acrylate, acrylamide, maleic anhydride,
The polymerization of at least one of vinyl benzenesulfonic acid sodium, Sodium Allyl Sulfonate, vinyl acetate, Isooctyl acrylate monomer is obtained.
6. a kind of method preparing microcapsules by polymer pre-coated according to claim 5, it is characterised in that：It is described
Core material is at least one of Rosa Damascana, caryophyllus oil, wide leaves of pulse plants oil, dicyclopentadiene, paraffin.
7. a kind of method preparing microcapsules by polymer pre-coated according to claim 6, it is characterised in that：It is described
Organic solvent is at least one of dichloromethane, chloroform, petroleum ether, tetrahydrofuran.
8. a kind of method preparing microcapsules by polymer pre-coated according to claim 7, it is characterised in that：It is described
Help colloid protective agent be dodecyl sodium sulfate, polyvinyl alcohol, polyvinyl pyrrolidone, Arabic gum, in methylcellulose extremely
Few one kind.
9. a kind of method preparing microcapsules by polymer pre-coated according to claim 8, it is characterised in that：It is described
Wall material is at least one of sodium alginate, polystyrene, Lauxite, phenolic resin, melamine resin.
10. microcapsules prepared by a kind of method preparing microcapsules by polymer pre-coated described in claim 9.
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| CN107118296B (en) * | 2016-10-13 | 2019-11-01 | 广西中烟工业有限责任公司 | A kind of macromolecule resin complex microsphere and preparation method thereof with controllable menthol covering amount |
| CN106955652A (en) * | 2017-04-11 | 2017-07-18 | 广州秘理普植物技术开发有限公司 | A kind of essence microcapsule and preparation method thereof |
| CN108794673B (en) * | 2018-07-02 | 2020-09-25 | 清华大学 | Phase-change material microcapsule and preparation method thereof |
| CN109897484A (en) * | 2019-01-26 | 2019-06-18 | 厦门申德欧新材料科技有限公司 | A kind of energy-accumulating luminous multifunctional coating and preparation method thereof |
| CN112089529B (en) * | 2020-08-24 | 2022-01-25 | 浙江珍琦护理用品有限公司 | Paper diaper capable of keeping skin clean and healthy |
| CN112169716A (en) * | 2020-09-09 | 2021-01-05 | 中国科学院山西煤炭化学研究所 | Preparation method of microcapsule coated with solid microparticles |
| CN113508810A (en) * | 2021-06-15 | 2021-10-19 | 上海大学 | Eugenol natural antibacterial microcapsule and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH09290146A (en) * | 1996-04-30 | 1997-11-11 | Fuji Photo Film Co Ltd | Micro capsule, its manufacture, and thermal recording material and mulrticolor thermal recording material using the micro capsule |
| CN102719227A (en) * | 2012-05-08 | 2012-10-10 | 广西桂邦生物能源有限公司 | Preparation method for high stable phase transition emulsion |
| CN104874339A (en) * | 2015-05-18 | 2015-09-02 | 江南大学 | Preparation method of double-layered wall material phase-variable micro capsule |
-
2016
- 2016-04-15 CN CN201610238903.2A patent/CN105854745B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH09290146A (en) * | 1996-04-30 | 1997-11-11 | Fuji Photo Film Co Ltd | Micro capsule, its manufacture, and thermal recording material and mulrticolor thermal recording material using the micro capsule |
| CN102719227A (en) * | 2012-05-08 | 2012-10-10 | 广西桂邦生物能源有限公司 | Preparation method for high stable phase transition emulsion |
| CN104874339A (en) * | 2015-05-18 | 2015-09-02 | 江南大学 | Preparation method of double-layered wall material phase-variable micro capsule |
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Address after: 510663 Unit 404, Level 4, C2 District, 182 Science Avenue, Science City, Guangzhou High-tech Industrial Development Zone, Guangdong Province Patentee after: MILIPU (Guangzhou) Plant Technology Development Co., Ltd. Address before: 510663 Unit 404, 4th Floor, C2 District, 182 Science Avenue, Science City, Guangzhou High-tech Industrial Development Zone, Guangdong Province Patentee before: Guangzhou Milim Plant Technology Development Co., Ltd. |